CN102597099A - Quick drying polymeric coating - Google Patents

Quick drying polymeric coating Download PDF

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Publication number
CN102597099A
CN102597099A CN201080010642XA CN201080010642A CN102597099A CN 102597099 A CN102597099 A CN 102597099A CN 201080010642X A CN201080010642X A CN 201080010642XA CN 201080010642 A CN201080010642 A CN 201080010642A CN 102597099 A CN102597099 A CN 102597099A
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weight
compsn
polymkeric substance
fertilizer
pva
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CN201080010642XA
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CN102597099B (en
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J·L·桑德斯
G·马佐
J·马佐
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Verdesian Life Sciences US LLC
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Specialty Fertilizer Products LLC
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Priority claimed from US12/351,589 external-priority patent/US20100175443A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C1/00—Ammonium nitrate fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C1/00—Ammonium nitrate fertilisers
    • C05C1/02—Granulation; Pelletisation; Stabilisation; Colouring
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • C05C3/005—Post-treatment
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • C05C9/005—Post-treatment
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings
    • C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/40—Fertilisers incorporated into a matrix
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/05—Bimodal or multimodal molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse

Abstract

Improved agriculturally useful products are provided, including solid materials such as nitrogenous fertilizers (e.g., urea), together with a polycarboxylated polymer selected from the group consisting of a salts of copolymers containing individual quantities of maleic and itaconic moieties. The polymer composition also includes from about 10-60% by weight of an organic drying agent such as a lower alcohol which enhances the quick drying properties thereof. The compositions may also include an amount of boron, and bimodal vinylic polymer made up of quantities of high and low molecular weight (MW) vinylic polymers such as PVA.

Description

Fast dried polymeric coatings
The cross reference of related application
The application is to be that January 9, application number in 2009 are that SN 12/351,589, denomination of invention are the part continuation application of " fast dry polymeric fertilizer additive " applying date.Be incorporated into this in first to file in full with reform.
Background of invention
Technical field
The present invention relates generally to improved agricultural quick drying paint compsn and method, wherein said compsn comprises (polycarboxylated) polymer salt and the organic siccative of volatility of one or more poly carboxylic acidization.More specifically; The present invention relates to such compsn and method; Wherein contain the toxilic acid of respective numbers and the multipolymer of methylene-succinic acid part and be aided with (supplemented) volatility siccative, it can mix with solid or be coated onto on the solid, and said solid for example is solid-state nitrogenous fertilizer.In another aspect of this invention; Through adding boron; Particularly add vinyl polymer simultaneously and in multipolymer-organic desiccant composition, be provided improved time of drying; Said vinyl polymer contains a large amount of functional pendant groups like alcohols, and optional lower molecular weight and HMW (MW) polymer moieties of comprising.
Description of the Prior Art
USP 6,515,090 has described a series of efficient multipolymer that good result is arranged in many agricultural application.Multipolymer and the salt of partly being processed by different ratios toxilic acid and methylene-succinic acid thereof has been described in ' 090 like patent, and this multipolymer and salt thereof can be used for solid fertilizer, improves output with big spoke.Generally speaking, the aqueous copolymer mixture is applied on the solid fertilizer to form fertilizer-polymer compsn through sprinkling or other method.
The professional fertilizer product Ltd (Specialty Fertilizer Products) in Kan. Li Wude city (Leawood) according to ' 090 patent commercialization a series of multipolymers.A kind of in these polymkeric substance; The Nutrisphere-N that promptly is used for particle nitrogen fertilizer is designed to be applied to multiple solid or particle nitrogen fertilizer especially, on urea, ammonium salt, MAP or DAP.This product is the solid aqueous liquid dispersion of about 40 weight %, contains the toxilic acid of 1: 1 ratio and the calcium salt multipolymer of methylene-succinic acid part, and pH is about 3.25-3.75.
Yet it is found that, above-mentioned compsn occurred can not successful Application problem, this mainly is the moisture content by solid fertilizer, unfavorable field applying method or adverse environmental factors such as high humidity, low temperature cause.Particularly, said composition sprayed or be deposited on the solid fertilizer outside surface, moisture can form the residual coating of solid polymer through the mass transfer evaporation.Yet if composition dries overlong time and make not complete drying of compsn, the product after applying is with intractable and use.In fact, in some cases, the moist relatively solid fertilizer that has applied moisture multipolymer possibly form aggregate in field fertilization equipment, thereby is difficult to perhaps can not said compsn evenly be sprinkling upon the field.
The mixture of some poly carboxylic acid fluidized polymers and organic solvent is known, sees USP 5,868,964, like acrylic acid polymer and methyl alcohol.Yet from the type of polymer of selecting for use and/or the reason of organic solvent aspect, polymkeric substance and solvent are incompatible basically, cause producing the viscous precipitate that is inappropriate in the Ru 2006101161 use.Polycarboxylic acid polymer salt (polycarboxylate polymer salt) does not generally form stable solution in high levels of organic solvents (for example methyl alcohol).
Therefore the improved product for agriculture that needs a kind of and fast dried poly carboxylic acid fluidized polymer to contact in this area, for example solid fertilizer to reduce polymer-coated and drying problems, can not influence the production benefit that uses this base polymer simultaneously.
Summary of the invention
The present invention has overcome the problems referred to above; Provide with various solids (for example fertilizer) and used or be applied in the improved fast dry composition that contains polymkeric substance on the various solids (for example fertilizer); Form fast dry composition and replenished the method for the solid phase prod (polymer-supplemented solid products) of polymkeric substance, and use the Ru 2006101161 of polymer-coated to be the method for soil application with the raising plant biomass.
Generally speaking, the Ru 2006101161 of the present invention compsn that contains polymkeric substance that comprises a certain amount of solid fertilizer and contact with solid fertilizer.Initial preparation and the compsn that contains polymkeric substance that contacts with fertilizer comprise salt (salt that promptly contains the multipolymer of independent quantity toxilic acid and methylene-succinic acid part) and the organic siccative of volatility or the solvent of poly carboxylic acid fluidized polymer.After this, the water volatilization that siccative exists together with major part is substantially free of these compositions usually so impose in the Ru 2006101161 in field, but is made up of the salt of fertilizer and residual multipolymer.Surprisingly, it is found that the polymer salt through selecting can mix with organic siccative of high density, form the stable liquid compsn that contains polymkeric substance, and do not have inconsistent problem in the prior art.Final Ru 2006101161 can prepare as follows: the surface that this compsn that contains polymkeric substance is applied directly to solid fertilizer; The amount that applies can improve the plant growth and the output characteristic of final Ru 2006101161, makes excessive moisture rapid evaporation from Ru 2006101161 simultaneously.This has guaranteed that this Ru 2006101161 can be used for the field and not had the previous problem that Ru 2006101161 ran into by common broadcast application method or similar approach.
The method of use of this Ru 2006101161 comprises in the adjacent soil of seed that compsn is applied to and sows with the nitrogen amount with routine or positive growing crop.
When in above-mentioned polymer-coated compsn, being aided with a spot of boron (common form), can further be improved the result with boric acid.Boron uses more favourable with the vinyl polymer with a large amount of functional pendant groups (for example alcohol), said vinyl polymer is Z 150PH (PVA) preferably.More preferably be that the form of vinyl polymer additive is corresponding bimodal polymers with HMW and low-molecular-weight ethylenic based polyalcohol part.
Confirm that Ru 2006101161 of the present invention can significantly improve crop yield, and the existence of organic siccative and other composition can not hinder or change the raising of output.
Embodiment
The present invention is based on this discovery: use is added in the middle of the solid phase prod or is applied in the fast dried polymeric composition on the solid phase prod, can improve solid product for agriculture such as chemical fertilizer.This siccative is convenient to and has been improved the evaporation of moisture from product surface, thereby uses easily.
In fact, all available polymeric composition of the present invention of any fertilizer is handled formation and the raising fertilization effect to reduce dust.But in preferred embodiment, band nitrogen or nitrogenous fertilizer can both improve according to the present invention.For example, urea, ammonium sulfate, an ammonium nitrate and composition thereof all are optimal selections of the present invention, and can arbitrary solid form such as spherolite, particle use.First-selected single solid fertilizer is a Granular Urea.
As previously mentioned, poly carboxylic acid fluidized polymer of the present invention is selected from the multipolymer of sour form or contains the toxilic acid of some amount and the part salt (partial salt) of methylene-succinic acid part.These polymkeric substance preferably exist with the form of part salt, can comprise the not mixture of salt of the same race.In fact, arbitrary required cationic moiety can be used for from initial acid polymer formation polymer salt, particularly basic metal, earth alkali metal, ammoniacal liquor and alkylamine (like the C1-C6 alkylamine, like triethylamine).Polymer salt of the present invention is preferably the aqueous liquid dispersion form, but non-aqueous organic dispersions also can use.
USP the 6th, 515 has been described alkaline multipolymer (basic copolymer) No. 090, and this patented claim is incorporated into this in full with reform.Usually, the salt of multipolymer need comprise about 10%-90% toxilic acid part (more preferably from about 25%-75%), and the methylene-succinic acid of corresponding about 90%-10% part (more preferably 75%-25%).Multipolymer also can contain except that toxilic acid and the part the methylene-succinic acid, like vinyl segment.Yet this other part can only account for about 7% amount at most, and just multipolymer need contain about 93% toxilic acid and methylene-succinic acid part.Preferably, multipolymer is gone up basically by toxilic acid and methylene-succinic acid and is partly formed.The salt of preferred especially such analog copolymer for the previous Nutrisphere-N that is used for solid nitrogenous fertilizer
Figure BPA00001426023700041
that describes more generally; The salt of this multipolymer is preferably formed as follows: add alkaline matter (like oxide compound, oxyhydroxide or the carbonate of Ca, Mg, K, Na) to form the water mixture of required pH, the common scope of pH is 1-4.
The organic siccative of volatility can be made up of one or more organic cpds, preferably is selected from organic pure and mild ketone, particularly C 1-C 4Alkyl alcohol.From the consideration of cost, property easy to use and vapour pressure, methyl alcohol is most preferred siccative.Yet more generally, siccative can be selected from one or more and under STP (STP) condition, has the organic cpds at least about the 40mmHg vapour pressure.This comprises many preferred lower alcohols, like methyl alcohol (127mmHg), and ethanol (59mmHg) and Virahol (42.7mmHg).
Selected siccative and polymer salt preferably mix the compsn that contains polymkeric substance with formation, and the said compsn that contains polymkeric substance is designed to be applied on the solid phase prod like nitrogenous fertilizer etc.In this case, the compsn that contains polymkeric substance generally includes dissolving, suspends or is dispersed in polymer salt and siccative in the aqueous liquid phase.The consumption of siccative is generally about 5 weight %-60 weight % (preferred about 30 weight %-50 weight %, most preferably from about 35 weight %-45 weight %) of the compsn that all contains polymkeric substance.Exist at the same time and use more high-load siccative possibly require through evaporation or other currently known methodss under the situation of high polymers solids concn water part or all remove basically from initial copolymer salt water-based material.So; The compsn that preferably contains polymkeric substance can comprise the copolymer salt of about 20 weight %-70 weight % (more preferably 30 weight %-60 weight %), the water (more preferably 10 weight %-25 weight %) of the siccative of about 30 weight %-50 weight % (more preferably 35 weight %-45 weight %) and about 10 weight %-50 weight %.The example that this kind contains the compsn of polymkeric substance contains the salt of toxilic acid-itaconic acid copolymer of about 40 weight %, the water of the methyl alcohol of about 45 weight % and about 15 weight %, and pH is 1-4, flash-point is 74 ℉.Usually, the flash-point of polymer compsn should be higher than 73 ℉.
In above-mentioned compsn, only replenish foregoing boron and will obtain more effect, boron more preferably combines with the bimodal ethylene based polyalcohol that contains HMW and low molecular weight part simultaneously." vinyl polymer (the vinylic polymer) " that use refers to any polymkeric substance or multipolymer here, and wherein most of recurring groups (group) are the vinyl alcohol part.Usually, the amount that the low-molecular-weight ethylenic based polyalcohol uses is higher than high-molecular weight, and typical high molecular weight material is about 1: 2 to 1: 20, more preferably from about 1: 4 to 1: 12 to the ratio of low molecular weight substance.
Typical vinyl polymer is PVA.Various PVA commercialization, and according to molecular weight and degree of hydrolysis differentiation, all from " low " to " height " classifies.That the number-average molecular weight Mn of lower molecular weight PVA is up to is about 15,000 (according to appointment 7,000-13,000), and weight-average molecular weight Mw is about 25,000 (according to appointment 13,000-23,000).These materials also have the degree of hydrolysis of about 98.0 moles of %-98.8 mole % and are about the viscosity of 3.5-4.5cps (20 ℃, 4% aqueous solution).The Mn of HMW PVA is about 70,000-101, and 000, Mw is 145,000 or higher (according to appointment 146,000-186,000), and degree of hydrolysis is 99.3+ mole %, and viscosity is about 62-72cps (20 ℃, 4% aqueous solution).
Usually, the MWD of business-like PVA or other polymkeric substance is in certain scope.MWD possibility broad or very narrow depends on given characteristics of product.Therefore; These mixture materials are represented with various molecular-weight average (number average or weight average) usually; This also helps to understand the character of product, all has the molecular weight close with molecular-weight average because account for the molecule and the major part in the example weight of significant percentage in the sample.Usually also represent the MWD in the polymkeric substance with figure, X-coordinate is represented molecular weight among the figure, and ordinate zou is represented the relative abundance of molecule.In the most polymers compsn; This figure is generally hump type; Contain a summit among the typical figure, modal molecular weight in the representation polymer compsn, this point is commonly called " peak molecular weight "; Refer to the molecular weight of a high proportion of polymer molecule, rather than the maximum molecular weight in the compsn.Yet bimodal ethylene based polymer compositions of the present invention has two humps or peak value on graph of molecular weight distribution.If this bimodal pattern system, can produce very wrong result with the metric words of molecular-weight average, because near the molecular amounts this " on average " value seldom.Therefore, bimodal or single peak type polymer compsn has identical molecular-weight average, but extremely different physical propertys is arranged.
Among the present invention, it is found that with the conventional composition that identical molecular-weight average is arranged and compare, the bimodal ethylene based polymer compositions better effects if of pbz polymer amount and low molecular weight part.Use the bimodal pattern compsn to obtain the optimal performance of HMW and low-molecular weight polymer.
Preferred bimodal pattern PVA is processed by the lower molecular weight and the HMW PVA of independent content, and the weight percent of lower molecular weight PVA is about the 0.5%-10% of whole fertilizer coating compositions, and the weight percent of HMW PVA is about 0.1%-4%.The content of lower molecular weight PVA than the height of HMW PVA, gets final product in foregoing HMW/low-molecular-weight ratio usually.
Well-known PVA is highly biodegradable water-soluble polymers, no matter is pure or in the aqueous solution, and a lot of characteristics are all arranged.These character possibly make PVA under a stable condition, be difficult to form mixture.Therefore, known PVA solvability in containing the solution of a large amount of organic solvents is very poor, and exists with precipitation forms.The PVA of height or superelevation degree of hydrolysis is all the more so, does not also dissolve in its solution that contains a large amount of organic solvents outside dewatering.Also known PVA can react rapidly with borate, forms the insoluble cross-linking plastic material that is commonly called as " plasticine (silly putty) " or " ooze (slime) ".
The PVA of height or superelevation degree of hydrolysis can be used for producing level and smooth and nonhygroscopic coating.Unfortunately, the agglomerative preparation takes place when being used to be manufactured on static (standing) in the very high and tendency of this PVA viscosity.Therefore this material itself is inappropriate for fertilizer coating purposes.On the other hand, low in hydrolysis degree PVA viscosity is low, but corresponding water absorbability is higher.
Unexpectedly, it is found that boron combines can avoid generating insoluble substance with selected PVA, and kept the water tolerance of HMW PVA and the LV of lower molecular weight PVA simultaneously to a great extent.Particularly preferably be bimodal pattern PVA compsn among this paper.
According to the present invention; Preferred complete fast dry polymeric compsn comprises: one or more foregoing toxilic acid-itaconic acid copolymers of (1) about 20 weight %-50 weight % (more preferably 35 weight %-45 weight %); Better the form with preferred part calcium salt multipolymer exists; And the used carboxylate salt of about 1%-35% (more preferably 10%-30%) is replaced by calcium, and corresponding pH is about 2.35-3.75 when multipolymer is in aqueous liquid dispersion; (2) volatile organic solvent of about 5 weight %-60 weight % (more preferably 35 weight %-50 weight %), particular methanol; (3) the lower molecular weight PVA of about 0.5 weight %-10 weight % (more preferably from about 2 weight %-6 weight %); (4) the HMW PVA of about 0.1 weight %-4 weight % (more preferably from about 0.2 weight %-2 weight %); (5) ratio of HMW PVA and lower molecular weight PVA is about 1: 2 to 1: 20 (more preferably from about 1: 4 to 1: 12); (6) boric acid of about 0.5 weight %-5 weight % (more preferably 2 weight %-4 weight %); (7) water of surplus in the compsn.This kind preferred coatings compsn contains the solid of 25 weight %-55 weight % usually approximately, more preferably from about 35 weight %-50 weight %.
Usually, bimodal PVA mixes with toxilic acid-itaconic acid copolymer, and is heated to about 80-110 ℃, and stirring for some time can dissolve to guarantee the PVA part.Then add organic siccative, and stir once more, add boric acid subsequently.In the preparation process, the water-based toxilic acid-itaconic acid copolymer mixture that solid content is about 35w/w% is put into reaction kettle and violent stirring in room temperature preferably.Lower molecular weight and HMW PVA add subsequently, and under the violent stirring that continues with mixture heating up to 97 ℃.Mixture can be cooked under 97 ℃ 45 minutes, all dissolved to guarantee PVA.Subsequently mixture vacuum distilling is reached required about 60w/w%-70w/w% until solid content, then mixture is cooled to room temperature.Methyl alcohol adds subsequently, and violent stirring to mixture is even.At last, add boric acid and also be stirred to dissolving fully once more.Last polymer compsn contains solid 40w/w% approximately.
Adding or do not adding under the situation of bimodal ethylene based polyalcohol and boron, the polymer compsn of processing by the salt and the siccative of aqueous copolymer can be arbitrarily easily method (like sprinkling, dip) be used for agricultural solid phase prod (like solid fertilizer).Preferred polymeric compositions has beyond thought and amazing consistency, and can not separate or be settled out solid.Usually, the consumption that contains the compsn of polymkeric substance is about the compsn that about 0.1-1 gallon in fertilizer per ton or other solid phase prod contains polymkeric substance (per ton contain about 0.3-0.8 gallon be good).
Though in a preferred form; Composition just being used for before the solid fertilizer coating composition mixes the formation the finished product; But also can respectively salt, siccative and other composition of multipolymer be used separately, particularly under the situation of all using simultaneously or using fast.In this case, consider two kinds of different compositions that apply material, it applies ratio can be same as described above.In addition, polymer compsn of the present invention can be used for multiple product for agriculture, like seed or soil improvement agent (soil amendments).
This fast dry composition also can be mixed with and comprise various dyestuffs, pigment, tinting material, tracer agent (tracing agent) etc.These methods are widely known by the people at agriculture field.The whole water prescription consistency of known many dyestuffs and high ionic strength is poor.Yet, have been found that the present composition of (appreciable) volatile organic constituents that contains appreciable amount replenishes this dyestuff more easily, and the existence of preferred PVA can improve its Color to solid fertilizer.
The fast dry composition that the present invention preferably contains polymkeric substance and the embodiment of method of use thereof are provided below.Yet this embodiment only draws example and does not limit overall range involved in the present invention as elaboration.
Embodiment 1
Be prepared as follows Ru 2006101161: the liquid compsn that will contain polymkeric substance puts on the granular urea, and it applies ratio is that urea per ton applies 1/2 gallon the liquid compsn that contains polymkeric substance (urea+water-based-methyl alcohol Nutrisphere-N
Figure BPA00001426023700071
).The compsn that contains polymkeric substance is made up of the salt of above-mentioned Nutrisphere-N multipolymer.
Another kind of Ru 2006101161 prepares as follows: water-based Nutrisphere-N
Figure BPA00001426023700073
product is put on the granular urea with above-mentioned same ratio, but do not use methyl alcohol siccative (urea+water-based Nutrisphere-N
Figure BPA00001426023700074
).
The fertilizer of last test is that the nothing of directly using applies urea (not having the urea of coating).
These three kinds of Ru 2006101161s are used for field test, to observe the influence of methyl alcohol siccative to output.This test in the mud loam of Kansas State Kao Telan city Ke Lite, carry out (Crete, Courtland, KS); Soil pH is 6.5; Organic content 2.2%, mine-laying P-1 (Bray P-one) scope is 19ppm, the K content that available ammonium acetate extracts in the test of soil potassium is 380ppm.The corn that no tillage system is irrigated was planted on 6 experimental plots with the ratio of every acre 32,000 strain May 2.The corn of plantation receives liquid just fertile (fertilizer starter) (10-34-0) with 8 gallons every acre ratio, and every capable edge strip executes 2 * 2.The water that the water barrow is irrigated is provided by the black Weir reservoir of drawing of the central and north, the Kansas State (Lovewell Reservoir).
Corresponding solid fertilizer compsn applies with two kinds of ratios: 160 and 240 pounds every acre nitrogen (lb.Nitrogen), and behind corn planting, sow immediately and use.Six experimental plots are: do not have urea/160 of coating pound nitrogen/acre; Urea+water-based Nutrisphere-N/160 pound nitrogen/acre; Urea+water-based-methyl alcohol Nutrisphere-N/160 pound nitrogen/acre; There is not urea/240 of coating pound nitrogen/acre; Urea+water-based Nutrisphere-N/240 pound nitrogen/acre; Urea+water-based-methyl alcohol Nutrisphere-N/240 pound nitrogen/acre.The nitrogen of introducing when irrigating, no longer add nitrogen in the soil except the water barrow.
Gathered in the experimental plot combine harvester November 2 in the experimental plot, two rows in the middle of the every experimental plot harvesting.Humidity is 15.5% o'clock record yield data.
Maize yield is consistent and meet statistical law (95% fiducial interval) very significantly with corresponding solid fertilizer.Do not compare the order of magnitude that the no tillage system maize yield of applying fertilizer with urea+water-based-methyl alcohol Nutrisphere-N improves and similar (table 1) that applies fertilizer with urea+water-based Nutrisphere-N polymkeric substance with the situation of applying fertilizer with nothing coating urea.
These data show that the salt coating urea with the high capacity density copolymer has very big influence to Maize Absorption nitrogen, thereby have improved corn yield and possibly the potential benefit arranged to corn.These data confirm that further siccative has no adverse effect to the effect of polymkeric substance-coating urea.
Table 1
Improve the nitrogen absorptivity of irrigating corn
Figure BPA00001426023700081
Figure BPA00001426023700091
*Duncan (Duncan) the multiple range inspection show average that there were significant differences
Embodiment 2
In this embodiment; Different compositions has been carried out a series of dry tests, and said compsn comprises the aforesaid Nutrisphere-N (being " polymkeric substance " of following table 2) that is used for particle nitrogen fertilizer.
Said preparation comprises the methyl alcohol of various quantity, and also has some to contain a small amount of boric acid.In addition, lower molecular weight and HMW PVA join in some prescriptions.Lower molecular weight PVA [Celvol 103, available from Seraing Ni Zi chemical company (Celanese Chemical)] has variable molecular weight, and degree of hydrolysis is 98.4 ± 0.4 moles of %, and viscosity is 4.0 ± 0.5cps (4% solution).HMW PVA (Celvol 165, available from Seraing Ni Zi chemical company) has variable molecular weight, and degree of hydrolysis is 98.4 ± 0.4 moles of %, and viscosity is 67 ± 0.5cps (4% solution).
In each test, the preparation of every corresponding polymer places Petri dish, and it is absolutely dry to be stirred to prescription with pipette tip then.Prescription and be recorded in table 2 time of drying.
Table 2
Figure BPA00001426023700093
Above-mentioned data show; Compare with the Nutrisphere-N
Figure BPA00001426023700094
of benchmark preparation 1, preparation 2,3 and 5 has improved time of drying.Surprisingly, compare with preparation 2, the adding of boric acid (preparation 3) has also significantly reduced time of drying.Preparation 5 has obtained optimum time of drying, comprises using bimodal PVA.This result is surprising, because preparation 5 contains obviously more water and similar solid content than preparation 2, preparation 3.
Infer that according to theoretical the formation of polymkeric substance-boron-PVA adducts has played synergy, thereby shortened time of drying.
Because of traditional particle nitrogen fertilizer product apply usually after harder and anti-moisture absorption, so comparatively speaking, the time of drying after the measurable preparation of Petri dish result of this test is applied on the solid nitrogenous fertilizer.

Claims (65)

1. compsn that contains polymkeric substance that is fit to be applied to agricultural solid phase prod, the described compsn that contains polymkeric substance comprises multipolymer and organic cpds siccative, described multipolymer comprises the toxilic acid part and the methylene-succinic acid part of independent quantity.
2. the compsn that contains polymkeric substance as claimed in claim 1 is characterized in that, described multipolymer comprises about 10%-90% toxilic acid part and about 90%-10% methylene-succinic acid part.
3. the compsn that contains polymkeric substance as claimed in claim 1 is characterized in that, described siccative is selected from organic pure and mild ketone.
4. the compsn that contains polymkeric substance as claimed in claim 3 is characterized in that described siccative is selected from C1-C4 alcohol.
5. the compsn that contains polymkeric substance as claimed in claim 1 is characterized in that, the content of described organic siccative is about 5 weight %-60 weight %.
6. the compsn that contains polymkeric substance as claimed in claim 1 is characterized in that described multipolymer is the form of part salt, and contains at least about 93% methylene-succinic acid part and toxilic acid part.
7. the compsn that contains polymkeric substance as claimed in claim 1 is characterized in that, described compsn comprises the methyl alcohol of the said multipolymer of the partial salt of about 20 weight %-70 weight %, about 5 weight %-60 weight % and the water of about 10 weight %-50 weight %.
8. the compsn that contains polymkeric substance as claimed in claim 7 is characterized in that, the content of the salt of described multipolymer is about 30 weight %-60 weight %, the about 30 weight %-50 weight % of methyl alcohol, the about 10 weight %-25 weight % of water.
9. the compsn that contains polymkeric substance as claimed in claim 1 is characterized in that, said compsn comprises the boron that about 0.5 weight %-5 weight % exists with the boric acid form.
10. the compsn that contains polymkeric substance as claimed in claim 9 is characterized in that, said compsn comprises a certain amount of bimodal ethylene based polyalcohol, and described bimodal ethylene based polyalcohol comprises independently HMW and low-molecular-weight ethylenic based polyalcohol part.
11. the compsn that contains polymkeric substance as claimed in claim 10; It is characterized in that; Described bimodal ethylene based polyalcohol comprises that weight-average molecular weight Mw is about 13,000-23, and 000 lower molecular weight PVA and weight-average molecular weight Mw are about 145; 000 reaches higher HMW PVA, and the amount of said lower molecular weight PVA is higher than the amount of HMW PVA.
12. the compsn that contains polymkeric substance as claimed in claim 11 is characterized in that, the ratio of described HMW PVA and lower molecular weight PVA is about 1: 2 to 1: 20.
13. the compsn that contains polymkeric substance as claimed in claim 12 is characterized in that described ratio is about 1: 4 to 1: 12.
14. a compsn that contains polymkeric substance that is fit to be applied to solid nitrogenous fertilizer, the described compsn that contains polymkeric substance comprises:
(1) about 20 weight %-50 weight % toxilic acid-itaconic acid copolymers, the form of said multipolymer are part salt and contain at least about 93% methylene-succinic acid part and toxilic acid part;
(2) content is about the volatile organic solvent of 5 weight %-60 weight %;
(3) content is about the lower molecular weight PVA of 0.5 weight %-10 weight %;
(4) content is about the HMW PVA of 0.1 weight %-4 weight %;
(5) be about the ratio of 1: 2 to 1: 20 HMW PVA and lower molecular weight PVA;
(6) content is about the boric acid of 0.5 weight %-5 weight %; And
(7) water.
15. the compsn that contains polymkeric substance as claimed in claim 14 is characterized in that:
(1) described toxilic acid-itaconic acid copolymer partly is made up of toxilic acid part and methylene-succinic acid basically, and exists with the form of part calcium salt, and carboxylate salt is about 1%-35% by the replacement amount of calcium, and the content of said multipolymer is about 35 weight %-45 weight %;
(2) described organic solvent comprises methyl alcohol, and the content of said organic solvent is about 35 weight %-50 weight %;
(3) content of described lower molecular weight PVA is about 2 weight %-6 weight %, and weight-average molecular weight is about 13,000-23,000;
(4) content of described HMW PVA is about 0.2 weight %-2 weight %, and weight-average molecular weight is about 146,000-186,000;
(5) described ratio is about 1: 4 to 1: 12;
(6) content of described boric acid is about 2 weight %-4 weight %; And
(7) water constitutes the surplus of said compsn.
16. the compsn that contains polymkeric substance as claimed in claim 1 is characterized in that, the salt of described multipolymer partly is made up of toxilic acid part and methylene-succinic acid basically.
17. the compsn that contains polymkeric substance as claimed in claim 1 is characterized in that, in the salt of described multipolymer, the ratio of toxilic acid part and methylene-succinic acid part is about 1: 1.
18. the compsn that contains polymkeric substance as claimed in claim 1 is characterized in that, the siccative of described selection is selected from the organic cpds that under STP condition vapour pressure is at least about 40mmHg.
19. the compsn that contains polymkeric substance as claimed in claim 1 is characterized in that, the described flash-point that contains the compsn of polymkeric substance is higher than 73 ℉.
20. Ru 2006101161 as claimed in claim 1 is characterized in that, the described compsn that contains polymkeric substance comprises the salt of the said multipolymer that is suspended in the some amount in the liquid phase, and described liquid phase comprises water and described siccative.
21. a fertilizer product, said fertilizer product comprises:
The solid fertilizer of some amount; And
Be applied to the compsn that contains polymkeric substance as claimed in claim 1 of said fertilizer.
22. fertilizer product as claimed in claim 21 is characterized in that, described fertilizer is nitrogenous fertilizer.
23. fertilizer product as claimed in claim 22; It is characterized in that; Described fertilizer is selected from urea, ammonium sulfate, an ammonium nitrate, MAP, the DAP of particle or pellets, and the consumption that imposes on the said compsn on said fertilizer surface is the said compsn that contains polymkeric substance of the about 0.1-1 gallon of said solid fertilizer per ton.
24. fertilizer product as claimed in claim 21 is characterized in that, described fertilizer is urea, and described compsn is a compsn as claimed in claim 14.
25. fertilizer product as claimed in claim 21 is characterized in that, described Ru 2006101161 is through the described composition sprayed that contains polymkeric substance is formed to described solid fertilizer.
26. fertilizer product as claimed in claim 21 is characterized in that, described multipolymer comprises about 10%-90% toxilic acid part and about 90%-10% methylene-succinic acid part.
27. fertilizer product as claimed in claim 21 is characterized in that, described siccative is selected from organic pure and mild ketone.
28. fertilizer product as claimed in claim 27 is characterized in that, described siccative is selected from C1-C4 alcohol.
29. fertilizer product as claimed in claim 21 is characterized in that, the content of described organic siccative is about 5 weight %-60 weight %.
30. fertilizer product as claimed in claim 21 is characterized in that, described multipolymer is the form of part salt, and contains at least about 93% methylene-succinic acid part and toxilic acid part.
31. fertilizer product as claimed in claim 21 is characterized in that, described compsn comprises the said multipolymer of the partial salt of about 20 weight %-70 weight %, the water of the methyl alcohol of about 5 weight %-60 weight % and about 10 weight %-50 weight %.
32. fertilizer product as claimed in claim 31 is characterized in that, the content of the salt of described multipolymer is about 30 weight %-60 weight %, and the content of methyl alcohol is about 30 weight %-50 weight %, and the content of water is about 10 weight %-25 weight %.
33. fertilizer product as claimed in claim 21 is characterized in that, said fertilizer product comprises the boron of the boric acid form of about 0.5 weight %-5 weight %.
34. fertilizer product as claimed in claim 33 is characterized in that, said fertilizer product comprises a certain amount of bimodal ethylene based polyalcohol, and described bimodal ethylene based polyalcohol comprises independently HMW and low-molecular ethylene polymers part.
35. fertilizer product as claimed in claim 34; It is characterized in that; Described bimodal ethylene based polyalcohol comprises weight-average molecular weight Mw and is about 13,000-23, and 000 lower molecular weight PVA and weight-average molecular weight Mw are about 145; 000 with the HMW PVA of Geng Gao, the amount of described lower molecular weight PVA is higher than the amount of described HMW PVA.
36. fertilizer product as claimed in claim 35 is characterized in that, the ratio of described HMW PVA and described lower molecular weight PVA is about 1: 2 to 1: 20.
37. fertilizer product as claimed in claim 36 is characterized in that, described ratio is about 1: 4 to 1: 12.
38. a method of giving soil application, described method comprises the step that fertilizer product as claimed in claim 21 is imposed on soil.
39. method as claimed in claim 38 is characterized in that, described fertilizer is fertilizer as claimed in claim 14.
40. method as claimed in claim 39 is characterized in that, described fertilizer is fertilizer as claimed in claim 15.
41. method as claimed in claim 38 is characterized in that, said method comprises the step of using said fertilizer, and the consumption of said fertilizer is the said compsn that contains polymkeric substance of the about 0.1-1 gallon of said solid fertilizer per ton.
42. method as claimed in claim 38 is characterized in that, described solid fertilizer is a urea, and the described compsn that contains polymkeric substance is a compsn as claimed in claim 14.
43. a method that forms Ru 2006101161, said method comprises following steps:
A certain amount of solid nitrogenous fertilizer is provided;
The compsn that will contain polymkeric substance imposes on the described solid fertilizer, and the said compsn that contains polymkeric substance comprises the salt and the organic cpds siccative of multipolymer, and the salt of said multipolymer contains the toxilic acid part and the methylene-succinic acid part of independent quantity.
44. method as claimed in claim 43 is characterized in that, described solid fertilizer is selected from urea, an ammonium nitrate, ammonium sulfate and their mixture.
45. method as claimed in claim 43 is characterized in that, described solid fertilizer is a particulate state.
46. method as claimed in claim 43 is characterized in that, the salt of said multipolymer comprises the toxilic acid part of about 10%-90% and the methylene-succinic acid part of about 90%-10%.
47. method as claimed in claim 46 is characterized in that, the salt of said multipolymer contains the toxilic acid part and the methylene-succinic acid part of about 1: 1 ratio.
48. method as claimed in claim 43 is characterized in that, described siccative is selected from organic pure and mild ketone.
49. method as claimed in claim 48 is characterized in that, described siccative is selected from C1-C4 alcohol.
50. method as claimed in claim 49 is characterized in that, described siccative is a methyl alcohol.
51. method as claimed in claim 43 is characterized in that, the described siccative of selecting for use is selected from the organic cpds that under STP condition vapour pressure is at least about 40mmHg.
52. method as claimed in claim 43 is characterized in that, said method comprises the step that the described compsn that contains polymkeric substance is applied over said solid fertilizer as topcoating.
53. method as claimed in claim 52 is characterized in that, said method comprises the composition sprayed of the described polymkeric substance step to the described solid fertilizer.
54. method as claimed in claim 43 is characterized in that, the described compsn that contains polymkeric substance comprises the salt of the multipolymer that is suspended in the some amount in the liquid phase, and described liquid phase comprises water and described siccative.
55. method as claimed in claim 54 is characterized in that, described siccative is a methyl alcohol, and the content of said methyl alcohol in Ru 2006101161 is about 10 weight %-60 weight %.
56. method as claimed in claim 55 is characterized in that, described content is about 35 weight %-45 weight %.
57. method as claimed in claim 56 is characterized in that, the described compsn that contains polymkeric substance comprises the methyl alcohol of the salt of the said multipolymer of about 20 weight %-70 weight %, about 10 weight %-60 weight % and the water of about 10 weight %-50 weight %.
58. method as claimed in claim 43 is characterized in that, the described compsn that contains polymkeric substance comprises the methyl alcohol of the salt of toxilic acid-itaconic acid copolymer of about 40 weight %, about 45 weight % and the water of about 15 weight %.
59. method as claimed in claim 43 is characterized in that, the described consumption that contains the compsn of polymkeric substance is the said compsn that contains polymkeric substance of the about 0.1-1 gallon of described solid fertilizer per ton.
60. method as claimed in claim 43 is characterized in that, the described compsn that contains polymkeric substance be water-based and pH be about 1-4.
61. method as claimed in claim 43 is characterized in that, the said compsn that contains polymkeric substance comprises the boron of the boric acid form of about 0.5 weight %-5 weight %.
62. method as claimed in claim 61 is characterized in that, said method comprises a certain amount of bimodal ethylene based polyalcohol, and described bimodal ethylene based polyalcohol comprises independently HMW and low-molecular-weight ethylenic based polyalcohol part.
63. method as claimed in claim 62; It is characterized in that; Described bimodal ethylene based polyalcohol comprises weight-average molecular weight Mw and is about 13,000-23, and 000 lower molecular weight PVA and weight-average molecular weight Mw are about 145; 000 with the HMW PVA of Geng Gao, the amount of described lower molecular weight PVA is higher than the amount of described HMW PVA.
64., it is characterized in that the ratio of described HMW PVA and said lower molecular weight PVA is about 1: 2 to 1: 20 like the described method of claim 63.
65., it is characterized in that described ratio is about 1: 4 to 1: 12 like the described method of claim 64.
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